Unlocking Strategic and Critical Raw Materials: Assessment of Zinc and REEs Enrichment in Tailings and Zn-Carbonate in a Historical Mining Area (Montevecchio, SW Sardinia)

Mining wastes are often both a potential source of Strategic and Critical Raw Materials (SRMs and CRMs) and a threat to the environment. This study investigated the potential of mining wastes from the Montevecchio district of Sardinia, Italy, as a source of SRMs and CRMs. The tailings from Sanna mine processing plant were characterized by X-ray diffraction, Scanning Electron Microscopy, and Plasma Mass Spectometry, showing contents of 1.2 wt% of lead, 2.6 wt% of zinc, and about 600 mg/kg of Rare Earth Elements (REEs). White patinas formed in the riverbed, composed by Zn-bearing minerals (hydrozincite and zincite), also contain about 2900 mg/kg of REEs. Characterization of white patinas along the Rio Roia Cani evidenced that their precipitation from water also involves an uptake of Rare Earth Elements, enhancing their contents by an order of magnitude compared with tailings. The process of REEs concentration in Zn-bearing minerals of white patinas is a candidate as a tool for the economic recovery of these elements. These findings suggest that mining wastes from the Montevecchio district could be considered a potential resource for extracting SRMs and CRMs

Adaptive strategies in populations of Chirocephalus diaphanus (Crustacea, Anostraca) from temporary waters in the Reatine Apennines (Central Italy)

To investigate the relationship between the adaptive strategies of Chirocephalus diaphanus (Crustacea, Anostraca) and the environmental characteristics of its habitat, we studied two populations living in high-altitude biotopes with very different characteristics, i.e. a semipermanent pool (Tilia Lake) and a temporary one (Illica Plain Pool), and we examined the essential features of their biological cycles (growth rate, reproductive biology, sex ratio and life cycle). The results show that the two populations adjust to the biotopes in which they live, fully exploiting the brief period available for development, in agreement with hypotheses formulated in studies of other colonizers of temporary environments. The strategy adopted by the Chirocephalus diaphanus population of Tilia Lake, a predictable and relatively constant environment, is similar to the k type, characterized by slow growth, late reproduction and a long life cycle. In contrast, the Illica Plain population presents rapid growth, precocious reproduction and a short life cycle, since it is highly dependent on the precariousness and unpredictability of the pool in which it lives

MINERALOGICAL STUDIES OF THE W-Sn VEIN SKARNS OF MONTE TAMARA (NUXIS, SULCIS DISTRICT): INSIGHTS FOR STRATEGIC MINERALS EXPLORATION IN SW SARDINIA (ITALY).

Skarn deposits are a relevant source of critical raw materials such as W, Sn, and In. Recent studies conducted in South Sardinia pointed out the relationships between various Sn-W-Mo deposits and the early Permian (289-286 Ma) F-bearing, ilmenite-series ferroan granites (e.g., Sulcis pluton). This new evidence triggered a broad re-examination of granite-related deposits including skarn deposits hosted by Cambrian limestones of the low-grade Variscan basement of the Sulcis district (SW Sardinia). With this purpose, field investigations and OM, SEM-EDS, EMPA, and LA-ICP-MS observations, and analyses have been conducted on the skarn ores of Monte Tamara (Nuxis, northern Sulcis) where scheelite has been reported in the old San Pietro and Sinibidraxiu mines. The San Pietro mine exploited a 1-5 m thick and 70 m deep, steeply dipping skarn orebody located at the tectonized contact between early Cambrian sandstones and limestones. The orebody includes layers of Grt-Cpx-Wo, magnetite, and Zn-Pb-Cu-Fe sulfide bands. Prograde and retrograde stages with oxides and sulfides can be recognized. Clinopyroxene is the foremost mineral of the prograde stage; garnets (andradite-grossular) are usually dark green with typical anomalous birefringence and distinctly zoned (Fe-rich cores and Al-rich rims). Hematite turned to mushketovite, and Mo-rich scheelite, followed by In-bearing cassiterite, occasionally occur in the prograde assemblages. Amphiboles and epidotes mark the retrograde stage, together with abundant Zn-Cu-Fe-Pb sulfides and accessory molybdenite, stannite, bismuthinite, and Bi-Ag-Pb sulfosalts. At San Pietro, dominant sphalerite displays highly variable Fe, Mn, and Cd contents. Relictlooking blebs of Fe-Mn-poor Sp are scattered in high-Fe-Mn Sp where Sn EMPA peaks may correlate with cassiterite-stannite micro-inclusions. Galena composition suggests localized intergrowths with micro-inclusions of bismuthinite, Bi-Se, and Bi-Te sulfosalts. The stannite-sphalerite geothermometer provided a temperature range of 325-200°C for the sulfide stage. The Sinibidraxiu old mine exploited a 1,5 m thick and 60 m deep columnar body, hosted in early Cambrian marbles. It consists of a sphalerite-wollastonite assemblage with late sulfides, quartz, and calcite, hosting cm-sized arsenopyrite and scheelite. Scheelite is Mo-poor; Sn-, other Mo-phases and Bi-phases are absent. High-Fe Sp, rimmed by low-Fe Sp and blebby galena, is finely intergrown with wollastonite cockades. The results from this study suggest that a wide range of skarn-related mineralizing phenomena occurred in the Monte Tamara area. Both orebodies resulted from a structurally controlled migration of metasomatic fluids inside the hosting carbonate formation. Mineral zonation and composition of the San Pietro skarn point towards skarn development under varying fO2 conditions, oxidizing then rapidly turning to moderately reducing within the prograde W-Sn skarn stage and into the sulfide stage. The features of the Sinibidraxiu orebody (e.g., Mo-poor, As-devoid scheelite) suggest a formation from reducing metasomatic fluids but S-poor compared to San Pietro, probably at more distal environments (e.g. low Sn-Bi contents). From this point of view, the Monte Tamara area still maintains an economic potential, linked to the possible presence of proximal skarn ores at depth; thereby representing a key area for further exploration for granite-related strategic and critical metals in SW Sardinia

Mineralogy of the scheelite-bearing ores of Monte Tamara, SW Sardinia: insights for the evolution of a Late Variscan W–Sn skarn system

Southwestern Sardinia, Italy, hosts several skarn, W–Sn–Mo greisen and hydrothermal deposits related to a 289±1 Ma Late Variscan granite suite. Among them, the most representative scheelite-bearing skarns belong to the San Pietro and Sinibidraxiu localities, in the Monte Tamara area, Sulcis region. The San Pietro deposit is a typical calc-silicate skarn whereas Sinibidraxiu is a sharply bounded orebody hosted in a marble unit. Optical petrographic observations and compositional data of major and trace elements were obtained for samples from both localities. San Pietro data suggests evolution from an oxidising prograde skarn stage (andradite–diopside, hematite and scheelite), to progressively more reducing conditions from the early retrograde (magnetite–cassiterite) to the late sulfide stage (arsenopyrite, stannite, molybdenite, Bi sulfosalts and Zn–Cu–Pb–Fe sulfides); Sinibidraxiu has diffuse carbonate–quartz intergrowths pseudomorphic over an early mineral assemblage with fibrous habit, followed by abundant ore mineral precipitation under reducing conditions (scheelite, arsenopyrite and Pb–Zn–Cu–Fe sulfides). Geothermometers indicate a comprehensive temperature range of 460–270°C for the sulfide stages of both deposits. The differences between the two deposits might be controlled by the distance from the source intrusion coupled with the different reactivity of the host rocks. The San Pietro mineralogy represents a more proximal skarn, contrasting with more distal mineralogical and chemical features characterising the Sinibidraxiu orebody (lack of Mo–Sn–Bi phases; LREE–MREE–HREE signature of scheelite). This investigation contributes for the first time to the identification of a W–Sn skarn system in SW Sardinia, thereby suggesting the Monte Tamara area and its surroundings as favourable for further exploration

PRELIMINARY STUDIES ON BIOPRECIPITATION PROCESSES MEDIATED BY SULFATE REDUCING BACTERIA (SRB) AND METAL IMMOBILIZATION IN MINE IMPACTED ENVIRONMENTS.

Mining activity often leaves a critical legacy represented by huge volumes of mine wastes and residues, usually made up of highly reactive materials, which lead to the mobilization and dispersion of harmful elements in soils and waters. Although these extreme environments are adverse to the development of living organisms, it has been observed that some microorganisms are able to adapt, playing a role in metal mobility, and becoming part of the resilience of the system itself. The Iglesiente and Arburese (SW Sardinia, Italy) mine districts, now abandoned, have been exploited for centuries by mining activities aimed at Pb-Zn extraction from sulfides and non-sulfides (calamine) deposits. Here, biogeochemical barriers naturally occur as an adaptation of the ecosystem to environmental stresses. Studies, from macroscale to microscale, showed that sulfate-reducing bacteria (SRB) may influence metal mobility by mediating the precipitation of secondary authigenic metal sulfides under reducing conditions. Specifically, framboids of Zn sulfides and Fe sulfides have been observed in the sections of stream sediments core characterized by the presence of abundant organic matter, especially residues of vegetal tissues (e.g. roots and stems of Juncus acutus and Phragmites australis). Laboratory-scale experiments were performed to better understand the bioprecipitation processes. For this purpose, anaerobic batch tests were carried out using high polluted mining waters (Zn and sulfate concentrations up to 102 and 103 mg/l, respectively) inoculated with native selected sulfate-reducing bacteria from stream sediments collected in the investigated areas. Dramatic decrease (up to 100%) in Zn and sulfate was observed in solutions. Moreover, scanning electron microscopy - energy dispersive spectroscopy (SEM-EDS) analysis, performed on solids recovered at the end of the experiments, showed the presence of precipitates characterized by a tubular morphology and made up by S and Zn. SRB inocula were studied by next-generation sequencing (NGS) approach, with the aim to compare the microbial diversity of the different SRB communities and to search for indigenous novel metal-tolerant sulfidogenic microorganisms. These findings represent a valuable step forward to plan effective bioremediation strategies for reducing metal mobility and dispersion. Also, bioprecipitation mediated by SRB can have great potentialities for metal recovery and our results can help to develop biomining techniques. The authors acknowledge CESA (E58C16000080003) from RAS and RAS/FBS (F72F16003080002) grants, and the CeSAR (Centro Servizi d'Ateneo per la Ricerca) of the University of Cagliari, Italy, for SEM analysis

Case Report HPV Type 6 and 18 Coinfection in a Case of Adult-Onset Laryngeal Papillomatosis: Immunization with Gardasil

Laryngeal papillomatosis (LP) is a rare human papillomavirus (HPV) related disease that often requires multiple surgical interventions and residual impairment of voice is almost inevitable. We report the case of a patient with adult onset recurrent LP, showing moderate dysplasia and coinfection with HPV types 6 and 18. The tetravalent HPV vaccine Gardasil was prescribed off label, with the aim of triggering an immunogenic response and consequently reducing the probability of further recurrences. The patient was followed for 9 months with no sign of relapse of his LP. The postexposure use of the anti-HPV vaccine could represent a promising therapeutic agent in established LP. Unfortunately, the potential efficacy of this new therapeutic option in this situation has been suggested only by isolated case reports. Further controlled studies, with a longer follow-up and a larger sample size, are needed to assess efficacy of Gardasil in LP

Natural attenuation can lead to environmental resilience in mine environment

Four streams flowing in the Iglesiente and Arburese mine districts (SW Sardinia, Italy), exploited for zinc (Zn) and lead (Pb) extraction from sulphides and secondary non-sulphide mineralization (calamine ores), have been studied combining investigations from the macroscale (hydrologic tracer techniques) to the microscale (X-ray powder diffraction, scanning electron microscopy, X-ray absorption spectroscopy). In the investigated area, concerns arise from release of metals to water during weathering of ore minerals and mine-waste. Specifically, Zn is observed at extremely high concentrations (10s of mg/L or more) in waters in some of the investigated catchments. The results from synoptic sampling campaigns showed marked differences of Zn loads, from 6.3 kg/day (Rio San Giorgio) to 2000 kg/day (Rio Irvi). Moreover, natural attenuation of metals was found to occur i) through precipitation of Fe compounds (Fe oxy/hydroxides and “green rust”), ii) by means of the authigenic formation of metal sulphides promoted by microbial sulphate reduction, iii) by metal intake in roots and stems of plants (Phragmites australis and Juncus acutus) and by immobilization in the rhizosphere, and iv) by cyanobacterial biomineralization processes that lead to formation of Zn-rich phases (hydrozincite and amorphous Zn-silicate). The biologically mediated natural processes that lead to significant abatement and/or reduction of metal loads, are the response of environmental systems to perturbations caused from mine activities, and can be considered part of the resilience of the system itself. The aim of this study is to understand the effect of these processes on the evolution of the studied systems towards more stable and, likely, resilient conditions, e.g. by limiting metal mobility and favouring the improvement of the overall quality of water. The understanding of how ecosystems adapt and respond to contamination, and which chemical and physical factors control these natural biogeochemical barriers, can help to plan effective remediation actions

Contributo alla conoscenza della fauna ad Anostraci (Crustacea, Branchiopoda) delle Puglie

ItUna campagna di campionamenti nelle pozze temporanee del Salento è stata effettuata negli inverni 2004 e 2005. La ricerca condotta arricchisce di nuovi dati le scarse notizie sulla distribuzione degli Anostraci in Puglia. Chirocephalus diaphanus e Branchipus schaefferi sono le due specie di acqua dolce presenti nel Salento. Degna di nota è la coesistenza delle due specie nel sito di Sandonaci (BR), che merita ulteriori indagini allo scopo di chiarirne i meccanismi.EnA series of collections, in Salento temporary ponds, has been carried out in winter 2004 and 2005. This research supplies with new data the scant knowledge on Anostraca distribution in Apulia. Chirocephalus diaphanus and Branchipus schaefferi are the Anostraca freshwater species so far known in Apulia. Their coexistence, in Sandonaci (BR), is very interesting and deserves further detailed field studies in order to understand the pattern of occurrence in the pool of these two wide- tolerant species

The Paleozoic basement of Monte Grighini Unit, a deep view in the nappe structure of Variscan belt in Sardinia. Synthesis of geological data and field guide

The Monte Grighini Complex (MGC; central-west Sardinia) is a metamorphic complex belonging to the Nappe Zone of the Sardinian Variscan belt, located at the northwestern end of the Flumendosa Antiform. It consists of three tectonic units, among which Monte Grighini Unit represent the deepest of the whole nappe zone, and a kilometer-wide shear zone with synkinematic granitoid intrusion. We present a guide for a two days field trip. The first day will be mainly focused on the metamorphic rocks of Monte Grighini Unit, and mylonitic leucogranite with S-C fabric together with other interesting structures (i.e. a giant quartz dyke). The second day will be developed along the mylonite/cataclasite belt on the southwestern side of the complex. The field guide is preceded by a brief, updated excursus on Sardinian Variscan basement and by a detailed description of the complex from the most recent papers

Geochemistry of the Monte Filau orthogneiss (SW Sardinia, Italy): insight into the geodynamic setting of Ordovician felsic magmatism in the N/NE Gondwana margin.

The Mt. Filau orthogneiss is an Ordovician orthogneiss outcropping in the External Zone of SW Sardinia chain. It consists of dark, biotite-rich facies, a leucocratic coarse-grained facies and a leucocratic fine-grained facies. Coarse- and fine-grained leucocratic orthogneiss have comparable major element contents, being slightly enriched in SiO2 and depleted in Fe2O3, MgO, TiO2 and CaO as compared to the Bt-bearing orthogneiss. Bt-bearing orthogneiss shows higher Sr and Ba concentrations than leucocratic ones, whereas Rb content is higher in leucocratic orthogneiss as compared to the Bt-bearing ones. Zr content shows a progressive decrease from Bt-bearing orthogneiss, coarse-grained leucocratic ones, to fine-grained orthogneiss. In the spider diagram the Mt. Filau orthogneiss shows the typical signature of calc-alkaline rocks, with negative anomalies of Ba, Nb, Sr and Ti, and positive anomalies in U, K. REE patterns of Bt-bearing and coarse-grained leucocratic orthogneisses are characterized by a moderate LREE fractionation, flat HREE and negative Eu anomaly. Fine-grained leucocratic orthogneiss shows flatter patterns, stronger Eu anomalies and slight HREE enrichment. The geochemical features suggest a clear evolution trend, from the less evolved Bt-bearing orthogneiss to the more differentiated fine-grained leucocratic orthogneiss which likely represent aplite bodies deriving from the most acidic residual melt. Selected trace and REE elements of Mt. Filau are compared with other Ordovician orthogneiss outcropping in the Axial Zone of Sardinia Variscan belt. Besides, their geochemical features are also compared with metavolcanics of External and Nappe Zone. The geochemical affinity of orthogneisses and metavolcanics from Variscan Sardinia, together with the geochronological data, allows to state a clear cogenetic relationship between the bodies belonging to the calc-alkaline Ordovician magmatic cycle. Our results suggest that the early Paleozoic basement of Sardinia might represents the witness of an early Paleozoic subduction-accretionary complex recording convergence along the N/NE Gondwana margin